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A S rUDY  OF  rHE  EXTRACTIVE  ACTION 
OF  BENZENE  AND  XYLENE  ON  COAL 
AT  HIGH  PRESSURES 


BY 

RICHARD  STONER  FISHER 


THESIS 


FOU  THE 


DEGKE1-:  OF  BACHEI.OR  OF  SCIENCE 


IN 


(HIEMISTRY 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 


UNIVERSITY  OF  ILLINOIS 


1922 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/studyofextractivOOfish 


- A 


The  writer  wishes  to  acknowledge  the  ready  advice 
and  helpful  criticism  of  Dr . T.  E.  Layng  in  the  work  of  which 
this  is  the  report. 


i 


TABLE  OE  CONTENTS 


Page. 


Introduction,  1. 

The  Carbonization  of  Coal.  2, 

Historical  2. 

Importance  of  Theory  of  Carbonization.  4. 

Methods  of  Attacking  the  Problem.  5. 

I.  The  Fractional  Carbonization  of  Coal.  7. 

II.  The  Action  of  Solvents  on  Coal.  10, 

Existing  Status  of  the  Theory  of  Carbonization.  12. 
The  Purpose  of  this  Investigation.  13. 

Experimental.  14. 

Conclusions,  17. 

Data.  19. 

Bibliography.  25, 


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A STUDY  OF 

THE  EXTRACTIVE  ACTION  OF  BENZENE  AND  XYLENE 
ON  COAL  AT  HIGH  PRESSURES. 

INTRODUCTION. 

The  primary  purpose  of  a study  of  the  products  obtained 
by  the  action  of  solvents  on  coal  is  to  formulate  a workable  the- 
ory of  coal  carbonization.  Of  all  industrial  operations  which  are 
carried  out  on  such  an  immense  scale,  the  manufact'ure  of  coke  is 
perhaps  the  least  understood.  In  spite  of  the  great  advance  the 
industry  has  made  in  substituting  the  by-product  recovery  oven  for 
the  older  bee-hive  type,  the  carbonization  of  coal  is  still  very 
largely  a rule  of  thumb  process. 

Why,  then,  a tneory  of  carbonizat ion?  Gooa  co^e  is 
made  by  the  present  methods.  One  - half  of  the  world’s  supply  of 
coal  is  in  the  United  States . What  need  is  there  of  knowing  the 
details  of  how  coke  is  formed  as  long  as  plenty  of  good  coke  can 
be  made  without  that  ^inowleage?  The  best  answer  to  this  query  is 
the  fact  tliat  at  the  present  rate  of  consumption,  the  available 
supply  of  coal  fit  for  coking  will  be  exhausted  in  the  next  fifty 
years.  Since  coal  is  such  a very  bulky  substance,  it  is  cheaper 
to  ship  iron  ore  to  the  country  which  produces  the  coal  than  to 
import  the  coal  necessary  for  metallurgical  processes.  Thus  no 
country  which  does  not  have  an  adequate  supply  of  coal  from  which 
good  metallurgical  coke  can  be  made  can  hope  to  be  a great  pro- 
ducer of  iron  and  steel  goods  no  matter  what  the  quantity  and  the 
quality  of  its  iron  ore. 


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It  is  imperative,  then,  if  we  wish  to  retain  our  pres- 
ent position  as  a great  steel  manufacturing  nation,  tmt  some 
method  he  found  to  coke  these  coals  which  are  at  present  regarded 
as  non  - coking.  Obviously  the  best  way  to  go  about  finding  why 
anthracites  and  some  of  the  lower  grades  of  coal  will  not  coke  is 
to  find  how  and  v/hy  the  so  called  "coking”  coals  do  form  coke. 

To  that  end  v?e  must  direct  our  attention  to  a study  of  the  devel- 
opment of  a theory  of  carbonization, 

THE  CARBONIZATION  OR  COAL, 

Coal  carbonization  aims  at  the  production  of  coke. 
According  to  V . B.  Lewes  (2)^,  coxe  is  "the  name  given  to  the 
solid  residue  left  by  the  destructive  distillation  of  coal  and 
many  other  carbonacous  substances,  and  contains  as  its  chief  con- 
stituent carbon,  together  with  the  mineral  matter  or  ash  of  the 
original  body,  such  portions  of  the  residues  as  the  tenperature 
employed  has  failed  to  drive  out  of  the  mass,  and  occluded  gasesV, 

HISTORICAL 

The  carbonization  of  coal  to  form  coke  grew  out  of  the 
necessity  of  finding  a substitute  for  charcoal.  Charcoal  had 
been,  up  to  this  time,  the  main  fuel  used  in  extracting  iron  from 
its  ores,  but  the  supply  of  wood  available  for  the  production  of 
charcoal  was  rapidly  being  exhausted.  The  first  attempts  to  coke 

coal  were  quite  naturally  patterned  after  the  methods  then  in 
general  use  in  charcoal  burning.  Cocil  was  heaped  on  the  ground, 
ignited,  and  plastered  with  wet  coal  dust  to  blanket  combustion. 

^N.  B.  Numbers  in  parenthesis  refer  to  bibliography. 


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Later  a sinall  chimney  was  introducea  in  the  center  of  the  coal 
mass  to  allow  free  escape  of  the  ^ases . The  pile  of  coal  was  ig- 
nited hy  introducing  burning  coal  through  this  chimney  and  com- 
bustion was  checlced  as  before.  This  method  of  coke  manufacture 
was,  of  course,  very  wasteful.  Not  only  the  gas  evolved  but  even 
a part  of  the  coal  itself  was  consumed  in  heating  the  mass.  The 
old  bee  - hive  coke  oven  grew  out  of  this  early  practice,  these 
ovens,  Duilt  in  groups  of  heavy  masonry,  had  the  effect  of  retain- 

I 

ing  the  heat  better  than  the  old  ”meiler”  heaps.  But  the  ovens 
were  still  heated  by  the  destruction  of  all  the  gaseous  products 
of  distillation  and  a part  of  the  coal  itself.  Gradually  we  have 
come  to  a realization  of  the  ijnmense  value  of  the  by  - products  of 
coal  distillation,  and  to  the  conviction  that  we  have  too  long 
been  wasting  our  natural  resources.  The  by  - product  coke  oven 
has  come  into  wide  use  as  a direct  result  of  this  feeling,  togeth- 
er with  the  greater  economy  of  operation.  These  ovens  are  fired 
externally  and  the  valuable  products  are  recovered  before  the  gas 
is  burned  to  heat  the  ovens. 

At  the  same  time  has  come  a somewhat  similar  development 
of  the  other  of  the  carbonization  industries  - gas  manufacture. 

The  growth  of  this  industry  has  been  marked  by  a doggeo  singleness 
of  purpose  which  has  at  times  overlooked  the  best  interests  of  the 
industry  as  a whole..  Gas  production  managers  have  been  intent 
upon  obtaining  the  largest  possible  volume  of  gas  from  a ton  of 
coal.  In  doing  this  they  have  frequently  been  guilty  of  forgetting 
quality  in  their  search  for  quantity.  They  have  also,  up  to  this 
time,  steadily  refused  to  devote  any  thought  to  a possible  improve- 
ment of  the  coke  produced  as  a by  - product  of  the  industry.  Coke 
in  the  gas  industry  has  always  been  considered  more  of  a necessary 


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evil  that  a possible  source  of  profit.  The  result  has  been  an 
inferior  quality  of  coke  - porous,  friable,  and  hard  to  dispose 
of.  It  is  to  be  hoped  that  the  gas  manufacturer  will  soon  take  a 
more  lively  interest  in  fuel  conservation  and,  by  using  a some- 
what lower  temperature  and  paying  a little  more  attention  to  the 
coke  produced,  give  us  a better  quality  of  gas  and^ample  quantity 
of  coke  which,  if  not  adaptable  to  metallurgical  uses,  may  be 
used  extensively  for  domestic  purposes.  Such  a coke  - cheap,  and 
easily  ignited  would  be  a boon  to  our  smoke  infested  cities. 

IMPORTANCE  OE  THEORY  OF  CARBONIZATION. 

What,  then,  is  the  problem  involved  in  the  theory  of 
carbonization?  Good  coke  is  being  made  every  day.  What  more  do 
we  want?  The  problem  is  simply  this.  Only  certain,  rather  def- 
initely restricted  classes  of  coal  will  coke.  Why  is  this?  What 
makes  coal  coke?  What  is  lacking  in  anthracites  tnat  they  will 
not  coke?  Why  will  lignites  not  coxe?  Can  these  non  - coking 
coals  be  made  to  coke?  These  are  some  of  the  questi  or.s  facing 
the  carbonization  industries  today.  Why  do  we  want  to  coke  these 
coals?  We  have  coal  enough  to  supply  us  with  metallurgical  coke 
for  many  years . Why  not  burn  the  rest  raw?  Because  when  raw 
coal  is  burned  in  the  ordinary  type  of  domestic  furnace  from  60  - 
80  % is  wasted.  V/orse,  for  this  waste  is  also  responsible  for  the 
great  smoke  nuisance  in  the  cities  and  so  impairs  the  cheerfulness 

and  even  the  health  of  the  inhabitants.  If  coke  were  used  exclu- 
sively for  domestic  and  office  heating,  great  wealth  in  the  form 
of  dye  - stuffs,  medicinal  basis,  germicides,  fertilizers,  and 
light  oils  for  use  as  a substitute  for  gasoline,  would  be  saved 


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METHODS  OE  ATTACKING  THE  PROBLEM. 

Three  methods  have  been  used  in  attacking  the  problem 
of  obtaining  a satisfactory  theory  for  the  carbonization  of  coal. 
These  are:- 

1.  Microscopic  examination . 

2.  Low  temperature  carbonization. 

3.  The  action  of  solvents  on  coal. 

Reinhardt  Thiessen  (3),  has  done  sojne  very  exact  work 
on  the  microscopic  examination  of  coal.  However,  since  this  phc^se 
of  the  work  has  more  bearing  on  the  ident if icat ion  and  examination 
of  the  individual  constituents  of  coal  than  on  any  definite  theory 
of  carbonization,  we  will  at  present  consider  the  last  two  means 
of  attack.  A very  interesting  theory  of  the  formation  of  coal 
has  been  built  up  around  this  work  of  Thiessen  by  David  V/hite  . (3) 
We  will  consider  -White’s  theory  a little  later  in  connection  with 
a preliminary  study  of  the  constitution  and  formation  of  coal. 

Before  starting  on  a review  of  the  work  that  has  been 
done  in  the  fields  of  low  temperature  carbonization  and  solvent 
action  it  will  be  well  to  present  some  of  the  ideas  and  accepted 
facts  concerning  the  substance  and  origin  of  coal.  What  is  coal? 
Where  did  it  come  from?  Almost  any  school  boy  will  embark  glibly 
enough  on  an  explanation  of  the  latter  question,  but  ask  him  what 
coal  is  and  he  has  no  answer.  Or  he  may  say  that  coal  is  carbon 
and  class  it  with  diamond  and  graphite  as  a form  of  that  element. 

As  a matter  of  fact  there  is  probably  no  free  carbon  in  coal.  And 
when  it  comes  to  an  attempt  to  enumerate  the  substances  present  in 
coal  we  may  as  well  admit  that  we  do  not  know.  We  only  know  that 
coal  contains  compounds  of  carbon,  hydrogen,  oxygen,  nitrogen,  and 
sulpher  arranged  in  innumerable  chemical  combinations  and  mixed 


iw-v-i  a»»«^  ^ *V'  A * *N»w  1 1 


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V '.■=»'  ^’'  ' .i«‘V 

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'■/  ’■■  ' \j  y,'  ■ ':  ” 

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*:  ,»',''i  J « ''''1*^'’-'  V'  < '•  VC*  _7»-V'  ■*-/^.'V..fji>v,.dO; 


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-6- 


with  inert  mineral  matter  in  varying  proportions.  This  complica- 
ted structure  of  coal  together  with  the  fact  that  coals  from  the 
same  neighborhood  may  be  widely  different  in  character,  is  very 
largely  responsible  for  the  altogether  different  results  which 
may  be  obtained  by  two  independent  investigators  working  on  simi- 
lar problems.  In  1878,  Green  defined  coal  as  "a  compact  stratified 
mass  of  mumified  plants  subjected  to  arrested  decay  in  various 
stages  of  completeness  and  free  from  all  except  a very  low  percent- 
age of  foreign  material". 

White  ( 3)  claims  that  all  coal  was  laid  do’vn  in  beds  an- 
alagous  to  our  peat  beds  of  today.  All  kinds  of  vegetation  from 
the  largest  club  mosses  to  the  smallest  fungi  went  into  the  depos- 
its. Hence  the  wide  divergence  in  the  characters  of  different 
coals  . The  climatic  conditions  existing  at  the  time  were  very 
largely  responsible  for  the  formation  and  burial  of  these  peat  beds 
The  warm  atmosphere  led  to  a quick  luxuriant  growth  which,  because 
of  the  coarse  structure  due  to  such  rapid  growth,  was  easily  at- 
tacked by  decay.  According  to  White,  one  foot  of  surface  peat  was 
laid  down  in  ten  years.  Because  of  dehydration  and  densif icat ion 
caused  by  the  increased  pressure  and  temperature,  it  would  take 
about  one  hundred  years  to  get  a one  foot  stratum  of  peat  twenty 
feet  below  the  surface  of  the  ground.  Three  feet  of  this  compress- 
ed peat  would  be  required  to  produce  a one  foot  stratum  of  coal. 

The  change  from  the  original  vegetable  matter  to  coal  is  divided 
into  two  parts.  First, the  dead  vegetable  matter  is  subjected  to 
biochemical  reactions  to  give  peat.  Then  the  peat  is  buried  and 
subjected  to  dynamo chemical  processes  to  form  coal.  Plant  mater- 
ials are  composed  chiefly  of  celluloses  and  proteins.  The  cellu- 
losic  part  makes  up  the  large  bulk  to  form  a framework.  The  pro- 





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Vt-tii.fi  n.'iJ  fESrC*/  . «4 ’’ lir.'j^^ 


-7- 


teins  are  concerned  in  the  vital  functions  of  the  plant.  These 
compounds  differ  widely  in  their  resistance  to  various  agencies. 
The  proteins  are  relatively  unstable  while  the  celluloses  are 
attacked  with  more  difficulty. 

At  the  death  of  the  plant,  governed  by  conditions  in 
the  bog,  a partial  decomposition,  elimination,  and  chemical  re- 
duction sets  in.  This  biochemical  change  is  brought  about  chief- 
ly by  organic  agencies  - fungi  at  first  and  bacteria  later.  The 
most  volatile  parts  of  t plant  constituents  are  removed  first, 
the  next  follow,  etc.,  until  the  most  resistant  parts  are  left  in 
a residue  called  peat.  This  process  of  decomposition  and  reduct- 
ion, begian  in  the  peat  cniefly  by  biochemical  means,  is  taken  up 
and  continued  by  dynamo chemi cal  agencies  into  and  through  succes- 
sive stages  of  de coiiposition  into  the  various  grades  of  coal. 

So  much  for  the  composition  and  formation  of  coal.  We  will  now 
turn  our  attention  to  the  most  common  methods  of  studying  coal 
carboni zati on, 

THE  FRACTIONAL  CARBONIZATION  OP  COAL. 

The  classic  example  of  carbonizati on  work  is  that  done 
in  England  by  Burgess  and  Wheeler  (4).  Similar  work  has  been 
more  recently  attempted  in  this  country  by  Porter  and  Tlaylor  (5), 
The  results  and  conclusions  drawn  by  Porter  and  Taylor  differ 
widely  from  those  of  Burgess  and  Wheeler.  This  does  not  mean  at 
all  that  the  results  of  one  or  tne  other  were  in  error,,  for  the 
experiments  were  both  carried  out  with  great  care,  but  it  does 
show  the  effect  of  a different  grade  of  coal  studied  under  slight 
ly  different  conditions  by  different  men.  The  personal  equation 
plays  an  important  part  in  such  studies  of  coal. 


I'"'  ir 


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1«" 


-8- 


Studying  the  gaseous  products  obtained  from  200  grams 
of  powdered  South  Yorks,  Silkstone  bituminous  coal  at  temperatures 
of  100’,  200’,  300*,  3t0*,  400’,  and  450’C,  Burgess  ana  Wheeler 
reached  the  following  conclusions: 

Coal  contains  two  types  of  compounds  of  different  de- 
grees of  ease  of  decomposition;  the  one,  the  least  stable,  yield- 
ing the  paraffin  hydrocarbons  and  no  hydrogen;  the  other,  decom- 
posing with  greater  difficulty  and  yielding  hydrogen  alone  or  hy- 
drogen and  the  oxides  of  carbon.  Probably  the  difference  between 
one  coal  and  another  is  determined  mainly  by  the  proportions  in 
which  these  two  types  of  compounds  exist,  anthracite,  for  example, 
containing  but  little  of  the  more  unstable  constituent.  The  pres- 
ence of  carbon  monoxide  is  more  probably  due  to  the  liberation  of 
water  from  hydroxy  compounds  and  the  subsequent  reaction  of  the 
steam  thus  formed  with  carbon.  In  a later  paper  Wheeler  states 
that  he  believes  that  the  hydrogen  yielding  constituent  is  what 
he  calls  the  "cellulosic"  and  the  paraffin  yielding  the  ’’resinic” 
part  of  the  coal.  The  experimental  work  of  Burgess  and  Wheeler 
has  been  confirmed  by  similar  work  carried  out  by  Vignon  on  some 
French  coals.  Vignon’ s discovery  of  a critical  temperature  be- 
tween 700’  and  800’C.,  at  which  there  is  a marked  increase  in 
the  evolution  of  hydrogen. 

The  conclusions  drav/n  by  Burgess  and  V/heeler  have,  how- 
ever, been  severely  criticised  by  Porter  and  Taylor(5).  These 
investigatorsaob j ect  to  the  statement  that  after  all  the  less 
stable  paraffin  yielding  ’’resinic”  constituent  has  been  decom- 
posed, tne  decomposition  of  tne  more  stable  hydrogen  yielding 

’’cellulosic"  part  sets  in  about  700’C.  Wheeler’s  statement  that 
water  of  decomposition  begins  to  be  evolved  about  200’C.,  shov/s 


T T -) 


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-9- 


that  a partial  decomposition  of  the  "cellulosic”  constituent  has 
"begun  at  that  early  point.  Porter  and  Taylor  found  that: 

1.  More  tiian  two  - thirds  of  the  organic  su’Dstance  of 
coal  is  decomposed  "below  bOO’C.,  but  there  is  a variation  among 
different  kinds  of  coal  in  their  ease  of  decomposition. 

2.  The  first  decomposition  occurring  in  any  type  of  coal 

as  the  temperature  is  raised  is  the  breaking  dov/n  of  certain  oxy- 
gen - bearing  substances  related  to  cellulose,  from  which  chiefly 
water  of  decomposition,  COj?*  CO.  are  produced, 

3.  Other  decompositions,  producing  paraffins  both  liq- 
uid a/h.  gaseous,  begin  at  an  early  stage.  Vlliether  or  not  such  de- 
compositions become  the  predominating  type  below  500’C.  depends  on 
the  character  of  the  coal,  and,  as  a general  rule,  the  higher  the 
oxygen  in  the  coal,  the  less  will  be  the  proportion  of  hydrocar- 
bons and  tax  in  the  volatile  matter. 

4.  Secondary  decompositions  of  the  primary  volatile  pro- 
ducts occur  quickly  and  easily  at  temperatures  of  730’C.,  and 
above. 

The  theoretical  conclusions  which  Porter  and  Taylor 
have  drawn  from  these  results  are  as  follows: 

"All  kinds  of  coal  consist  of  cellulosic  degradation 
products  more  or  less  altered  by  the  processes  of  aging,  together 
with  derivatives  of  resinous  substances,  vegetable  waxes,  etc.,  in 
different  proportions  more  or  less  altered.  They  all  undergo  de- 
composition by  a moderate  degree  of  heat,  some,  however,  decom- 
posing more  rapidly  than  others  at  the  lower  temperatures.  The 
less  altered  cellulosic  derivatives  decompose  more  easily  than 

the  more  alteied  derivatives  and  also  more  easily  tiisn  the  resin- 
ous derivatives.  The  cellulosic  derivatives  decompose  so  as  to 


A 


-10- 


yield  water,  caroon  monoxide,  carbon  dioxide,  and  hydrocarbons, 
giving  less  of  the  first  three  products  the  more  matured  and  alt- 
ered they  are.  The  resinous  derivatives,  on  the  other  hand,  de-e 
compose  on  moderate  heating  so  as  to  yield  principally  the  par- 
affin hydrocarbons,  with  probably  hydrogen  as  a direct  decomposi- 
tion product.  The  more  mature  bituminous  coals,  having  good  cok- 
ing properties,  contain  a large  percentage  of  resinous  derivatives, 
and  their  cellulosic . constituents  have  been  highly  altered.  The 
younger  bituminous  or  sub  - bituminous  coals  are  constituted  of 
cellulosic  derivatives  much  less  altered  than  those  in  the  older 
coals.  They  undergo  a large  amount  of  decomposition  below  their 
fusion  point  and  possibly  for  that  reason  many  of  them  do  not  coke! 


THE  ACTION  OF  SOLVENTS  ON  COAL. 


parts: 


The  study  of  solvent  action  should  be  divided  into  two 


1.  The  action  of  reagents  which  separates  out  some  of 
the  constituents  of  coal  in  an  altered  form.  Under  this  head  come 
sulphuric  and  nitric  acids,  potassium  and  sodium  hydroxides,  py- 
ridine, aniline,  quinoline,  phenol,  bromine,  and  oxygen. 

2.  True  solvent  action  which  is  believed  to  extract 
from  the  coal  substance  some  of  the  unchanged  coal  constituents. 
Some  of  the  substances  which  are  supposed  to  exert  only  a solvent 
action  on  coal  are  benzene,  chloroform,  alcohol,  ether,  petroleum, 
ether,  acetone,  toluene,  xylene,  and  di  - phenyl  ether. 

The  action  of  reagents  we  must  pass  over  without  much 

discussion.  No  results  obtained  from  a study  of  bodies  extracted 

from  coal  by  such  reagents  ceui  carry  much  weight  because  the  ex- 
istance  of  such  bodies  as  such  in  coal  cannot  be  definitely  proved 


t i. 


I . ■ 


I s 


i i ’ . -»■» 


■n  • 

.'iOV.  - -i- 

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-11- 


For  instance,  it  has  heen  found  that  the  substarice  obtained  from 
coal  by  extraction  with  pyridine  usually  contains  almost  twice  tne 
amount  of  nitrogen  as  was  originally  present  in  the  coal . This 
shows  that  the  pyridine  oase  has  entered  into  combination  with 
some  of  the  acidic  substances  of  the  coal  maicing  any  further  study 
of  the  products  obtained  useless. 

In  regard  to  solvent  action,  Bone  (l)  says: 

» The  difficulty  is  to  find  solvents  that  will  differen- 
tiate sufficiently  between  the  main  constituents  of  the  coal  and 
extract  a large  proportion  of  some  one  of  them,  without  at  the 
same  time  having  some  depolymerising  or  other  sinilar  action  upon 
the  whole  structure".  Most  of  the  solvents  which,  without  much 
question,  do  extract  the  coal  constituents  unchanged  do  so  in 
such  minute  quantities  as  to  make  the  task  of  obtaining  sufficient 
amounts  of  the  substances  for  experimental  purposes  almost  hope- 
less, J.  A.  Smythe  (1)  found  that  ethyl  ether  and  petroleum  e- 
ther  had  very  little  effect  on  the  coal  while  benzene,  chloro- 
form, and  alcohol  extracted  quantities  varying  between  1.8  and 
3.0  percent  of  the  coal.  Similar  experiments  have  been  more  re- 
cently carries  out  by  many  v/orkers  with  practically  the  seone  re- 
sults , 

Interesting  possibilities  are  disclosed  in  some  recent 
work  by  Fischer  and  Gluud  (1)  in  Berlin  on  the  action  of  benzene 
on  coals  at  pressures  of  some  50  atmospheres.  By  using  a temper- 
ature of  270’ C,,  and  a pressure  of  55  atmospheres,  6.7  % of  ex- 
tract was  obtained  from  a coal  which  had  previously  yielded  only 
0.1  % on  extraction  with  boiling  benzene.  No  study  of  the  pro- 
ducts obtained  was  made  aside  from  the  determination  of  their 
physical  properties.  No  proof  was  offered  that,  at  the  temper- 


-12- 


atures  employed,  decomposition  did  occur  except  that  no  gas  was 
noticed  on  opening  the  cooled  homb.  In  one  of  the  experiments, 
hydrogen  sulphide-  gas  was  noticed  on  opening  the  bomb.  This  was 
taken  as  an  indication  that  some  decomposition  had  occurred.  This 
work  of  Pischer  and  Gluud,  however,  undoubtedly  opens  up  great 
possibilities  of  finding  a means  of  obtaining  sufficient  quanti- 
ties of  such  extracts  from  coal  for  farther  experimental  work. 

EXISTING  STATUS  OF  THE  THEORY  OF  CARBONIZATION. 

The  existing  theories  of  coal  carbonization  have  been 
very  well  crystallized  in  the  following  statement  of  Lewes’  opin- 
ion: 

"Many  theories  have  been  put  forward  as  to  the  nature 
of  the  binding  material  in  coke.  Some  declare  tl^iat  it  is  the  re- 
siduum of  the  semi  - fused  constituents  in  coal,  whilst  Wedding 
and  others  consider  that  it  is  carbon  deposited  by  the  decomposi- 
tion of  heavy  hydrocarbon  vapors,  v;hich  is  undoubtedly  the  cause 
of  the  carbon  hairs  found  in  coking.  It  seems  most  probable,  how- 
ever, that  the  cementing  material  is  due  to  liquid  products,  the 
most  volatile  of  which  are  driven  off  as  vapors,  leaving  pitch, 
which  carbonizes  and  binds  the  mass  into  coke". 

A somewhat  different  theory  has  been  recently  aavanced 
by  Dr.  T.  E.  Layn^  of  the  University  of  Illinois, 

For  the  formation  of  good  coke  three  conditions  must 
be  fulfilled. 

1.  There  must  be  a bond  forming  material  present. 

2.  The  material  to  be  bonded  must  have  delivered  all 


of  the  adsorbed  oxygen  and  oxides  of  carbon  before  the  decorapo- 
^This  theory  was  presented  in  class  room  discussion. 


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-13 


sition  of  the  bond  forming  material. 

3.  The  bond  forming  material  must  not  distil  without 
decomposition. 

As  may  be  readily  seen,  this  theory  conforms  well  to  a 
number  of  well  known  facts  about  the  coking  of  coal.  Anthracites 
will  not  coke  because  they  lack  the  bond  forming  material.  The 
better  grades  of  bituminous  coals  conform  to  all  three  conditions 
and  therefore  give  good  coke . The  lower  grades  of  bituminous 
coals  and  lignites  are  easily  oxidizable.  Oxygen  is  adsorbed  and 
the  oxiaes  of  carbon  are  formed.  These  gases  are  liberated  at 
the  time  of  the  decomposition  of  the  bond  forming  material  and 
prevent  good  contact  of  the  bonding  material  with  the  material  to 
be  bonded. 


THE  PURPOSE  OF  THIS  INVESTIGATION. 

The  purpose  of  this  investigation  is  two  - fold: 

First,  to  find,  if  possible  some  method  of  extracting 
the  coking  constituent  from  coal  in  satisfactory  quantities  and 
with  as  little  change  as  possible. 

Second,  to  investigate,  with  the  aid  of  the  substances 
obtained  from  the  coal,  the  above  theories  of  carbonization. 


fJ  M,m 


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-14- 


exp  ERIMENTAL  ^ 

Extraction  of  Coal  with  Benzene  under  Pressure. 

Various  forms  of  bomhs  were  t.ried  in  the  heginning  of 
this  work.  The  first  type  used  was  a small  model  of  the  steel 
tomb  used  by  Fischer  and  Gluud.  A seven  inch  length  of  four  inch 
steel  pipe  was  threaded  at  both  ends  and  fitted  with  caps.  A 
mixture  of  litharge  and  glycerine  was  used  as  a cementing  agent 
and  later  lead  was  melted  into  tne  caps  in  an  attempt  to  make  the 
bomb  leak  - proof,  but  tne  pressure  desired  could  not  be  main- 
tained. In  the  second  attempt  several  ten  inch  lengths  of  one 
inch  pipe  welded  at  one  end  and  fitted  with  a cap  at  the  other 
were  used.  This  type  was  also  discarded  because  the  capacity  was 
too  small  and  leaks  still  developed.  The  most  satisfactory  re- 
sults obtained  were  with  tne  use  of  an  empty  mercury  container. 
100  grams  of  coal  powdered  to  pass  a sixty  mesh  sieve  and  about 
two  liters  of  benzene  were  charged  into  the  bomb  and  the  plug 
screwed  in  tightly  and  sealed  with  a smoothly  mixed  paste  of 
litharge  and  glycerine.  This  bomb  was  found  to  be  almost  entire- 
ly leak  - proof  at  the  pressures  used.  The  analysis  of  the  coal 
used  which  was  from  Franklin  County,  Illinois,  is  given  in  Table 
' 1 , of  the  section  devoted  to  data.  The  bomb  was  placed  in  an 
electric  furnace  and  kept  at  a temperature  of  from  210’  to  240’C. 
for  24  - 48  hours,  (see  table  2).  At  the  end  of  this  time  the 
bomb  was  opened  and  tne  solvent  was  decanted  off  rapidly  through 
a suction  filter  leaving  as  much  of  tne  coal  as  possible  in  the 
bomb.  Any  coal  on  the  filtor  was  returned  to  the  bomb  and  fresh 
solvent  was  added  as  before.  The  benzene  solution  of  the  third 


’' : ' ' ■ , ■„  •::’  mm 


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of  these  extractions  was  practically  colorless  showing  that  all 
of  the  material  extractable  with  benzene  was  reirioved  in  the  first 
two  extractions.  The  benzene  solution  of  the  extract  was  strongly 
fluorescent.  This  solution  was  again  filtered  to  remove  the  last 
traces  of  suspended  coal  and  evaporated  to  dryness  in  a current  of 
nitrogen.  The  residual  coal  after  the  last  extr section  was  W8.shed 
on  the  filter  with  alcohol,  then  with  ether  and  dried  in  a cur- 
rent of  nitrogen.  The  proceedure  in  the  case  of  the  extractions 
with  xylene  was  exactly  the  same  excepting  that  seven  extractions 
were  necessary  to  completely  exhaust  the  coal  of  extractable  ma- 
terial. The  results  (see  table  3),  show  that  in  the  case  of  the 
xylene  extractions  approximately  one  - fourth  of  the  coal  sub- 
stance was  disolved  out  of  the  coal  under  conditions  of  temper- 
ature and  pressure  which  preclude  any  possibility  of  decomposi- 
tion of  either  the  coal  or  the  solvent. 

The  comparison  between  the  ultimate  analysis  of  the 
coal,  extract,  a.nd  residue  shows  a close  agreement  in  the  values 
obtained  for  the  analysis  of  the  coal  by  actual  experiment  and 
by  calculation  from  the  corresponding  values  of  the  extract  and 
residue.  The  value  obtained  for  sulpher  is  too  low.  This  may 
be  ascribed  to  a loss  of  some  of  the  more  volatile  organic  sul- 
pher compounds  due  to  exposure  to  the  temperature  necessary  to 
drive  off  the  last  traces  of  the  xylene  from  the  extract.  The 
values  for  oxygen  and  hydrogen  reflect  the  high  heat  value  caused 
by  some  of  the  solvent  not  removed  from  the  residue  and  possibly 
from  the  extract.  The  analysis  of  the  residue  was  corrected  for 
an  ash  value  which  was  too  high,  due  to  extraneous  material  from 
the  bcanb  and  the  litharge  glycerine  mixture  used  to  seal  it. 


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I'i'A, 


16 


The  carbonization  data  (see  Tables  5 and  6)  is  of 
interest  both  as  a support  of  Dr.  Layng’s  tneory  of  carbonization 
and  as  farther  evidence  in  the  controversy  between  Burgess  and 
Wheeler  on  the  one  hand,  and  Porter  and  Taylor  on  the  other.  The 
main  constituents  of  the  gases  obtained  from  a carbonization  of 
the  residue  up  to  350* C,.  are  oxygen  and  carbon  dioxide.  Between 
350’  and  450’C.,  the  residue,  which  corresponds  to  what  Wheeler 
calls  the  ” cellulosic"  part  of  coal,  yields  mainly  hydrogen,  oxy- 
gen, and  the  oxides  of  carbon  together  with  quite  a large  percent- 
age of  hydrocarbons  of  the  marsh  gas  series.  In  the  carboniza- 
tion of  the  residue,  the  evolution  of  hydrogen  sulphide  was  first 
noticed  at  420’C.  No  tar  was  noticed  in  the  distillation  of  the 
residue. 

The  fraction  of  gases  collected  from  the  extract  up  to 
350’C.,  contained  mainly  hydrocarbons  of  the  marsh  gas  series 
with  appreciable  quantities  of  hydrogen,  carbon  monoxide  and  oxy- 
gen. The  fraction  from  350’  - 450’C.,  consisted  mainly  of  hydro- 
gen with  some  hydrocarbons.  Hydrogen  sulphide  evolution  began  aL 
240’ C.  A large  quantity  of  tar  of  specific  gravity  less  tnan  one 
was  collected. 

Various  coking  tests  were  made  and  are  tabuleb  od  after 
Table  6 in  the  data. 


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-vu.  , ■.  i'  i i'iSiitii.  . . . ‘' •■■■■'**  t;.  »#-“•'  .«■  '? 

"''■^  . ' '"Sr"  V,,  ^.ji■:^^^,'rJit^^' f: 

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v;‘434-i  . . 


-’TTA 


-17 


CONCLUSIONS, 

1.  In  the  opinion  of  the  writer,  the  most  important 
result  obtained  in  this  investigation  was  the  discovery  of  a new 
method  of  extracting  the  coking  constituent  of  coal  in  quantities 
large  enough  for  experimental  purposes.  The  coking  tests  made 
were  all  upon  one  gram  samples  and  as  such  are  possibly  not  en- 
tirely indicative  of  the  results  which  may  be  obtained  on  larger 
samples.  The  writer  believes  that  work  along  the  line  herein  ex- 
plained will  go  on  in  these  laboratories  and  that  extractions  will 
probably  be  made  on  several  kilos  of  coal  at  a time  in  autoclaves 
using  xylene  as  a solvent.  In  this  way  enough  of  the  coking  con- 
stituent could  be  obtained  in  the  course  of  several  weeks  to  per- 
mit more  exhaustive  investigations, 

2.  The  results  obtained  from  the  fractional  carboniza- 
tion of  the  extract  and  residue  seem  to  indicate  tJriat  both  sides 
are  right  in  the  controversy  between  Burgess  and  Wlieeler,  end 
Porter  and  Taylor.  The  main  constituents  of  the  gas  obtained 
from  the  residue  up  to  3fcO*C.,  are  oxygen  and  the  oxides  of  car- 
bon. The  largest  single  constituent  of  the  gas  from  the  residue 
between  350  and  450* C.,  is  hydrogen,  in  accordance  with  the  claims 
of  Burgess  and  Wheeler.  The  extract,  in  the  lower  fraction,  yields 
mainly  the  paraffin  hydrocarbons  as  is  agreed  by  both  factions, 
but  in  the  fraction  from  350*  - 450*0.,  the  main  constituent  is 
again  hydrogen  which  agrees  with  the  results  of  Porter  and  Taylor, 
but  is  contradictory  to  those  of  Burgess  and  Wheeler. 

The  sharp  distribution  of  organic  and  pyritic  sulpher 

between  the  extract  and  the  residue  is  shown  by  the  fact  that  the 
evolution  of  hydrogen  sulphide  from  the  extract  begins  at  240*0., 


-18- 

while  in  the  case  of  the  residue  it  is  not  apparent  until  420’ C,, 
is  reached. 

The  coking  tests  which  were  made  tend  to  substantiate 
the  theory  of  carbonization  which  has  already  been  attributea  to 
Dr.  Layng  of  this  University.  The  residue  from  the  xylene  extract 
ion  showed  no  coking  tendency  whatever.  This  shows  the  effect 
produced  when  the  bond  forming  niateris.1  is  removed.  When  the 
extract  and  residue  were  mixed  in  the  correct  proportions,  a good 
hard  coke  was  obtained.  Oxidized  residue  mixed  with  the  correct  m 
amount  of  extract  gave  a very  soft  sooty  coke.  After  carboniza- 
tion some  of  this  ixidized  residue  was  again  mixed  with  extract  a 
and  yielded  a good,  hard  coke.  This  test  show’s  the  effect  of  oxy- 
gen on  the  residue  where  it  is  unprotected  by  the  extractable  por- 
tion. Oxygen  is  adsorbed  and  combines  with  the  coal  substance. 
Oxygen  and  the  oxides  of  carbon  are  liberated  at  the  temperature 
of  decomposition  of  the  bond  forming  material  and  tend  to  pre- 
vent the  formation  of  a suitable  bond. 


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iv  t.*j  p’  X4* , , pi;  ■ i ti 

si-fc'-  :.S-JJ,:^-i  'Oiw  ‘li'  li  .Si^'^4-^ij(.‘»(M<j,^® 


j-  io;\.,t  aaAdi=|:.rv<’t' 

,'  ' ' ' ' ..  ' ..V. ‘'..r- 'll'  ■' 


' '.iii  •f)  .j-4 


■-wit  ;•«■«» 3 

.'  . ‘ *■  . . L«  iS»''.i.iL.^  . i'^5'..'it« 


-19- 

DATA 

Table  1, 

The  Proximate 

and  Ultimate  Analysis 

of  the  Coal  Used. 

Co  al 

from  Franklin  County, 

Illinois. 

As  received 

Moisture  and  ash  free. 

Moisture 

.9  .48 

- 

Ash 

9 .45 

- 

Volatile  matter 

38.58 

47.63 

Fixed  carbon 

42.49 

52.37 

B.  T.  XT. 

11,701. 

14,446. 

Carbon 

63.70 

78.64 

Hydrogen 

4.96 

6.02 

Oxygen 

9.42 

11.64 

Nitrogen 

.97 

1.21 

Sulpher 

2.02 

2.49 

k I I'jV,  'll  ^,»m-in?f-  ■'•- — 


* r •, 

* «•  * ♦ 


. .7 

1 


v’lrv 

^ >.  ■'* ',  I 


A#4: 


‘ y 


t 


.fi;p  affix' 


'»■'.•  ' ",«  ':  k,'  , , ' ■'■' 


» 

a. 


. :.•  zt  ’id  ri^.i'i  £)J I- :.  © « i J *a  X O' ' 


y. 


do:^ 

;.  . II 

iS..  - 


i 


l^viV‘r.5^  AA  • 

■y 

■'  ’ T'  > 


r ,V.  ^ 


^ : ',ic 


' -i’' 

^ ■''* 

• W .XV  ? ' ;-  -i 


-20- 


Table  2. 

Extraction  Data. 


Extraction 
with  Benzene 


Extraction 
with  Xylene, 


210  - 240»C.  210  - 240»C. 

250-37 b #/sq.in.  180-200  #/sq.in. 


lOOgm. 


lOOgm. 


Temperatin’es  used 
Pressure 

Weight  of  coal  used 
Humber  of  charges  of  solvent 
for  each  extraction 
Volume  of  solvent  used  in  each  charge 
Extraction  time  for  each  charge 

(■♦  A third  charge  of  benzene  was  introduced  into  the  bomb 
in  an  attempt  to  make  a more  complete  extraction  but  after 
extraction  the  solvent  was  only  slightly  discolored.) 


2 liters 
24-48  hrs . 


2 litei-s 
24-48  hrs. 


Table  3. 

Comparative  Yield  of  Extracts  obtained 
from  Benzene  and  Xylene. 

Percentage  original  coal  obtained 
as  extract , 

Benzene  Xylene. 


As  r * c *d  . 

M . & A.  free 

As  r’c’ 

First 

Extraction 

4.8 

6.0 

Second 

Extrtict  ion 

5.3 

6.6 

Third 

Extraction 

22.91 

Fourth 

Extract!  on 

24.85 

M & A 
free 


28.2 

30.7 


■ry ^ 


J X’  *-  u :>■'■■!; To 

•I  1 '.  '■ 

,.,  ' ;■  ■-.  ' :'x^‘  " ' 

; - .,  „.  i . . :-v  V ‘i  0 fei  a 1^’  * o V 

; i '0  / ''■^'/;*vCi,4  ^ ■ . 1 ■■  V 

0 '’■  v^;  :■;  . " y .v  , 


•'  * . lili. 


. ft  I ^ 

4)5  .‘;x  ■■.v'^-0  ■•'  ' ■ '.'.  ••  X,  ' - »''. 


•’  * . titi.  V •• 

V’  ljh,l 


v"  ;.  i:\J  , ’ 

v.'U'.Vi  nO'C  ^ 


't 


1 


;■..  Xr/'-'irX-'  )-:.  C.T 


21 


Table  4, 

A Comparison  of  the  Ultimate  analysis  of  Coal, 
Extract,  and  Residue, 


Xylene 

Residue 

Coal 

extract 

As  r*  c’d 

Corrected 
ash  basis 

calculated 
from  extract 
and  residue 

Coal  by 
analysis 

c 

85.96 

54.42 

57.28 

63.90 

63.70 

H 

7.13. 

- 

5.99 

6.20 

4.96 

0 

5.42 

- 

13.29 

11.43 

9.42 

N 

.42 

.98 

1.04 

.89 

.97 

S 

.95 

1 .50 

1.58 

1.44 

2.02 

Moist . 

.07 

6.96 

7.33 

- 

9.48 

Ash 

ol5 

17.53 

13.50 

- 

9.45 

B.  T.  U. 

16,499, 

10,667, 

11,229. 

12,387. 

11,701*. 

: ./  • 


i 

' 2 


r T 


I 

I 


t 

?♦ 

•::n 


\ 

f 


-22 


Fractional  Carbonization  of  Extract, 

Five  gram  sample  of  xylene  extract. 

Sulpher  begins  to  decompose  at  240’ C. 

Heavy  yield  of  light  tar  from  200  - 220'C, 

TabUe  5, 

Analysis  of  Gaseous  Products  of  the  Carbonization  of  Extract, 


Gases  up 

to  350’C. 

350  - 450’ 

C. 

Nitrogen  free 

Vol . in  e . c . 
from  100  gm  .ext . 

Nitrogen 

free 

Vol.  in  cc 
from  lOOgm 

C02 

4.9 

94 

4.1 

177 

°2 

12.6 

237 

-2.6 

110 

Unsat . 

4.7 

86 

.7 

31 

Aromatics 

.8 

14 

.4 

18 

20.3 

382 

53.3 

2275 

CO 

10.8 

202 

4.7 

201 

CH4 

19.6 

367 

23.6 

1007 

26.3 

497 

10.5 

433 

■V 


r 


I 


x.c- 


t 


[I 


» 


-23- 

Fractional  Carbonization  of  Residue. 

Sulpher  begins  to  decompose  at  420* C. 

Table  6. 

Analysis  of  Gaseous  Products  of  Carbonization  of  tbe  Residue, 


Gases 

up  to  350*C. 

350  - 

450*C. 

Nitrogen 

free 

% 

Vol . in  e .c . 

from  100  gm. 
of  extract. 

Nitrogen 

free 

% 

Vol , in  c. c 
from  100  gm 
of  extract. 

o 

o 

60.7 

646 

16.1 

540 

^2 

30.8 

277 

15.5 

518 

Unsat , 

.5 

4 

2.8 

92 

Aromatics 

.0 

0 

.5 

14 

«2 

1.8 

17 

38.4 

1285 

CO 

3.7 

34 

5.9 

199 

CH 

4 

.9 

8 

13.3 

447 

2 6 

1.6 

13 

7.5 

249 

9 


, f '• 


*•''*•'  I ^ 


l': 


'<;K 

01' 


>t-X 


!\  , 


V'  > 


1 


'>  ■' 


-24- 


Coking  Tests, 

A.  With  "benzene  extract  and  residue. 

Extraction  with  benzene  did  not  visibly  impair 
the  coking  qualities  of  the  residue. 

Benzene  extract  melts  from  115  - 130*C. 

B.  With  xylene  extract  and  residue. 

Residue  from  xylene  extraction  shows  no  coking 
tendency . 

100  % extract  softens  quickly  and  swells  to  a very 
great  extent.  Much  of  a one  gram  sample  will  be  lost  by 
this  swelling.  A light,  porous,  fluffy  coke  remains. 

15  % extract  85  % residue  gives  a rather  poor, 
soft  coke. 

30  % extract  70  % residue  gives  a hard,  black, 
porous  coke. 

Compares  favorably  with  coke  of  original  coal 
except  that  some  of  the  silvery  luster  is  lacking. 

A portion  of  the  residue  was  set  aside  and  exposed 
to  the  action  of  the  air  and  moderate  heat.  After  sev- 
eral weeks  of  this  atmospheric  oxidation  a coke  test  was 
made  with  70  % of  this  oxidized  residue  and  30  % ex- 
tract. The  mixture  shov/ed  only  a very  slight  caking 
tendency.  The  coke  obtained  was  very  soft  and  sooty. 

Some  of  this  oxidized  residue  was  then  heated  in  a cov- 
ered crucible  to  coking  temperature  and  a portion  mixed 
with  extracts  as  before.  Again  a coke  sample  of  good 
quality  and  texture  was  obtained. 


-25- 

BIBLIOGRAPHY. 

1,  Wm.  A.  Bone.  Coal  and  its  Scientific  Uses. 

2.  V.  B.  Lewes.  The  Carhonizat ion  of  Coal. 

5.  White  and  Thiessen.  The  Origin  of  Coal.  Bulletin 

38  Bureau  of  Mines.. 

4.  Burgess  and  Wheeler.  The  Volatile  Constituents  of 

I 

Coal.  Journ.  Chem.  Soc.  V.  97,  p.  1917;  V.  99, 
p.  649;  V.  105,  p.  131/. 

5.  Porter  and  Taylor.  The  Primary  Volatile  Products 

of  Coal.  Tech.  Paper  140,  Bureau  of  Mines. 

6.  Porter  and  Ovitz.  The  Volatile  Matter  of  Coal. 

Bulletin  1,  Bureau  of  Mines. 

7.  Parr  and  Hadley.  The  Analysis  of  Coal  with  Phenol 

as  a Solvent.  Journ.  Soc.  Chem.  Ind.  1915,  p.  213 
U.  of  I.  Engineering  Experiment  Station,  Bulletin  76 

8.  Lavid  White.  Effect  of  Oxygen  in  Coal. 

Bulletin  29,  Bureau  of  Mines. 

9.  Parr  and  Olin.  The  Coking  of  Coal  at  Low  Temperatures 

Engineering  Experiment  Station,  Bulletin  79, 


